Increasing Distillates Yield in Low Temperature Cracking Process by Using Nanoparticles of Solid Acids

ABSTRACT

Solid acid nanoparticles are added to crude oil before initial distillation in order to increase the yield of light hydrocarbons obtained during initial distillation. According to one aspect, nanoparticles of a solid acid of a characteristic particle size are added to crude oil before initial distillation in order to increase the yield of light hydrocarbons obtained during initial distillation. According to another aspect, nanoparticles of a solid acid are added to crude oil in a characteristic concentration before initial distillation in order to increase the yield of light hydrocarbons obtained during initial distillation. According to another aspect, nanoparticles of two or more solid acids are mixed and added to crude oil before initial distillation in order to increase the yield of light hydrocarbons obtained during initial distillation.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates broadly to the distillation of crude oil(petroleum) or a fraction of crude oil distillation. More particularly,this invention relates to methods of increasing the distillates yieldduring distillation of an unprocessed (raw) hydrocarbon composition byadding nanoparticles of various solid acids to the unprocessedhydrocarbon composition.

2. State of the Art

For much of the last century, crude oil (petroleum) has been one of theprimary sources of energy world-wide. Crude oil contains primarilyhydrocarbons. One of the major uses of crude oil is in the production ofmotor fuels such as gasoline and diesel. These motor fuels are obtainedthrough the refining of crude oil into its various component parts.Refining results in the production of not only gasoline and diesel, butkerosene and heavy residues.

Refining of crude oil is typically accomplished by boiling at differenttemperatures (distillation) and using advanced methods to furtherprocess the products which have boiled off at those differenttemperatures. The chemistry of hydrocarbons underlying the distillationprocess is that the longer the carbon chain of the hydrocarbon componentof the crude oil, the higher the temperature at which that componentboils. As a result, a large part of refining involves boiling atdifferent temperatures in order to separate the different fractions ofcrude oil and other intermediate streams.

As previously mentioned, crude oil or petroleum contains a mixture of avery large number of different hydrocarbons, most of which have between5 and 40 carbon atoms per molecule. The most common molecules found inthe crude oil are alkanes (linear or branched), cycloalkanes, aromatichydrocarbons and more complicated chemicals like asphaltenes. Eachpetroleum variety has a unique mix of molecules which define itsphysical and chemical properties.

The alkanes are saturated hydrocarbons with straight or branched chainswhich contain only carbon and hydrogen and have the general formulaC_(n)H_(2n+2). The alkanes from pentane (C₅H₁₂) to octane (C₈H₁₈) aretypically refined into gasoline (petrol). The alkanes from nonane(C₉H₂₀) to hexadecane (C₁₆H₃₄) are typically refined into diesel fueland kerosene which is the primary component of many types of jet fuel.The alkanes from hexadecane upwards (i.e., alkanes having more thansixteen carbon atoms) are typically refined into fuel oil andlubricating oil. The heavier end of the alkanes includes paraffin wax(having approximately 25 carbon atoms) and asphalt (having approximately35 carbon atoms and more), although these are usually processed bymodern refineries into more valuable products as discussed below. Thelighter molecules with four or fewer carbon atoms (e.g., methane), aretypically found in the gaseous state at room temperature.

The cycloalkanes are also known as naphthenes and are saturatedhydrocarbons which have one or more carbon rings to which hydrogen atomsare attached according to the formula C_(n)H_(2n). Cycloalkanes havesimilar properties to alkanes but have higher boiling points.

The aromatic hydrocarbons are unsaturated hydrocarbons which have one ormore planar six-carbon (benzene) rings to which hydrogen atoms areattached.

Although just about all fractions of petroleum find uses, the greatestdemand is for gasoline and diesel. While the amount (weight percentage)of hydrocarbons in the crude oil samples which through a simpledistillation ends up in gasoline and diesel varies widely depending uponthe geographical source of the crude oil, typically, crude oil containsonly 10-40% gasoline and 20-40% of diesel. Increasing gasoline anddiesel yield from a particular crude oil sample may be done by cracking,i.e., breaking down large molecules of heavy heating oil and residues;reforming, i.e., changing molecular structures of low quality gasolinemolecules; and isomerization, i.e., rearranging the atoms in a moleculeso that the product has the same chemical formula but has a differentstructure, such as converting normal heptane to isoheptane.

Generally, the simplest refineries undertake first-run distillation thatseparates the crude oil into light (gas, naphtha and gasoline), middle(kerosene and diesel) and heavy (residual fuel oil) distillates. Thesesimple refineries may include some hydrotreating capacity in order toremove sulfur, nitrogen, and unsaturated hydrocarbons (aromatics) fromthe distillates, and may also include some reforming capabilities. Thenext level of refinery complexity typically incorporates crackingcapabilities and some additional hydrotreating in order to improvedistillates quality; i.e., increasing the octane number for gasolinefractions and decreasing the sulfur content for gasoline and diesel. Themost complex refineries add coking, and more hydrotreating andhydrocracking.

The catalytic cracking process utilizes elevated heat and pressure andoptionally a catalyst to break or “crack” large hydrocarbon moleculesinto a range of smaller ones, specifically those used in gasoline anddiesel components. In other words, the cracking produces lighthydrocarbons from heavy hydrocarbons, for example, gasoline and kerosenefrom heavy residues. Typically, a mixture of gases (hydrogen, methane,ethane, ethylene) is also produced in cracking of heavy distillates.Likewise, a residual oil may be produced by the conventional crackingprocess.

Cracking of heavy hydrocarbons without a catalyst requires the use ofhigh pressures and temperatures, e.g. pressures of 600-7000 kPa andtemperatures of 500°-750° C. With a catalyst, the temperatures andpressures may be lower, e.g. 480°-530° C. and moderate pressure of about60-200 kPa. However, even at these relatively lower temperatures andpressures, a separate unit must be built to accommodate the process.

During cracking the hydrocarbon molecules are broken up in a fairlyrandom manner to produce mixtures of smaller hydrocarbons, some of whichhave carbon-carbon double bonds. A typical reaction involving thehydrocarbon might be:

C_(n)H_(k)=C_(n-m)H_(k-1)+C_(n-p)H_(k-q)+C_(m+p)H_(l+q)

Catalytic cracking generally uses solid acids as the catalyst,particularly zeolites. Zeolites are complex aluminosilicates which arelarge lattices of aluminium, silicon and oxygen atoms carrying anegative charge which are typically associated with positive ions suchas sodium ions. The heavy hydrocarbon (i.e., large molecule alkane) isbrought into contact with the catalyst at a temperature of about 500° C.and moderately low pressures (e.g., 60−200 kPa). The zeolites used incatalytic cracking (e.g., ZSM-5, Y, and E) are chosen to yield highpercentages of hydrocarbons with between 5 and 10 carbon atoms which areparticularly useful for generating petrol (gasoline).

SUMMARY OF THE INVENTION

According to one aspect of the invention, nanoparticles of a solid acidare added to crude oil in a characteristic concentration before initialdistillation in order to increase the yield of light hydrocarbonsobtained during initial distillation.

According to another aspect of the invention, nanoparticles of a solidacid of a characteristic particle size are added to crude oil beforeinitial distillation in order to increase the yield of lighthydrocarbons obtained during initial distillation.

According to an additional aspect of the invention, nanoparticles of twoor more solid acids are mixed and added to crude oil before initialdistillation in order to increase the yield of light hydrocarbonsobtained during initial distillation.

According to yet another aspect of the invention, solid acid micropowderis added to a crude oil residue after a partial initial distillation toincrease the yield of diesel oil resulting from the completed initialdistillation.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a flow diagram of a first method for implementing theinvention.

FIG. 2 is a flow diagram of a second method for implementing theinvention.

FIG. 3 is a flow diagram of a third method for implementing theinvention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Turning now to FIG. 1, according to a first method for implementing theinvention, at step 10, nanoparticles of a solid acid are added to andmixed into crude oil before the crude oil is subjected to distillation.At step 20, the crude oil with the nanoparticles of solid acid issubjected to a first stage distillation. The result of the first stagedistillation, as described in more detail below, is that an increasedyield of gasoline and diesel (light hydrocarbons) is obtained than wouldotherwise be obtained if the nanoparticles of solid acid had not beenadded to the crude oil. It is believed by the inventors that thenanoparticles of solid acid act to catalytically crack some of thelarger molecule hydrocarbons at relatively low temperatures (i.e., thedistillation temperatures of gasoline and diesel).

As described in more detail hereinafter, the nanoparticles of solid acidutilized at step 10 have a characteristic size of preferably between 3nm and 1100 nm, and more preferably between 30 nm and 600 nm and/orconstitute a concentration weight percentage of preferably between0.005% and 0.2%, and more preferably between 0.01% and 0.06% of thecrude oil/nanoparticle mixture. Also, as described in more detailhereinafter, the solid acid nanoparticles utilized at step 10 may bevarious types of solid acids (including micropowders) or combinationsthereof. The preferred size and concentration of the nanoparticles whichmaximizes the percentage of light hydrocarbons yielded during initialdistillation is believed to be at least partially dependent on the typeof solid acid and/or the combination of solid acids utilized.

As shown in Table 1, three different samples of crude oil were initiallyobtained. To avoid the common problem of 1% gas being present in thecrude oil, the crude oil was first heated at 70° C. for two hours. Firstportions of each sample were distilled as a control using a standardtest method for distillation of petroleum products at atmosphericpressure (i.e., European Standard EN 228 and ASTM D2892-05 Standard TestMethod for Distillation of Crude Petroleum (15-Theoretical PlateColumn)) as presented below.

TABLE 1 Yield of distillation fractions for three different samples ofcrude oil. Boiling range % w/w Fraction (° C.) Sample 1 Sample 2 Sample3 Gases up to 40 1 — — Petrol and naphtha  40-180 13 18 22 Diesel180-360 22 31 27 Residue above 360 64 51 51

To test the method set forth in FIG. 1, nanoparticles of solid acid werethen added to additional portions of the samples according to the methodset forth in FIG. 1 to form mixtures of crude oil/solid acidnanoparticles. The mixtures were then subjected to the same distillationprocedure as the controls.

Example 1

Zeolite Y powder with an average particle size of 600 nanometers wasadded to second portions of the samples so that the Zeolite Ynanoparticles constituted 0.01% by weight of the nanoparticle/crude oilmixtures. As shown in Table 2 below, upon distillation using the sameprocedure as described above with respect to the controls, the yields oflight hydrocarbons increased significantly over the yields of thecontrols (Table 1). The addition of Zeolite Y powder to all three crudeoil samples in a concentration of 0.01% improved the yield of petrol andnaptha by 3% and of diesel by 5-6%.

TABLE 2 Changes of the light fractions yield after adding 0.01% ofzeolite Y powder. Boiling range Change of yield, % w/w Fraction (° C.)Sample 1 Sample 2 Sample 3 Petrol and naphtha  40-180 +3 +3 +3 Diesel180-360 +6 +5 +5

Concentration tests were conducted with Zeolite Y powder (still with anaverage particle size of 600 nanometers). The Zeolite Y was added inconcentrations varying from 0.0005% to 0.3% to additional portions ofSample 1 as shown in Table 3 below. Upon distillation using the sameprocedure as described above with respect to the controls, the yields oflight hydrocarbons increased over the yields of the Sample 1 control.More particularly, the yields of light hydrocarbons remained the samewith a Zeolite Y concentration of 0.0005%, increased slightly for dieselusing a concentration of 0.001%, and markedly increased for bothpetrol/naphtha and diesel using a concentration of 0.01%. It isinteresting to note that the yield of light hydrocarbons was the sameusing a Zeolite Y concentration of 0.1%, 0.2%, and 0.3% as it was usinga concentration of 0.01%. Based on these results, it is expected thatthe preferred range of concentrations for Zeolite Y powder having anaverage particle size of 600 nanometers is between 0.001% and 0.3%, andmost preferably between 0.01% and 0.3%. It is anticipated based on thisdata that concentrations larger than 0.3% may also be used to improvethe yield of light hydrocarbons relative to the yield of the control(e.g., since the residue yield did not increase between concentrationsof 0.01% and 0.3%). At concentrations above 0.01%, the yield of lighthydrocarbons does not depend on the concentration of solid acid.Therefore, the yield saturates at 0.01% of solid acid. This value givesthe lower limit at which we obtain the best yield of light hydrocarbons

TABLE 3 Effect of the Zeolite Y concentration on the yield ofdistillation fractions for crude oil Sample 1. Concentration, % w/wFraction 0 0.0005 0.001 0.01 0.1 0.2 0.3 Petrol and naphtha 13 13 13 1616 16 16 Diesel 22 22 24 29 29 29 29 Residue 64 64 62 54 54 54 54

Example 2

Sulphated zirconia dioxide (super acid) having a particle size of 3.1nanometers was added in seven different concentrations to crude oil andthe resulting mixtures were distilled as discussed above. The yields andresidue resulting from these mixtures after initial distillation areshown in Table 4. As shown, increasing the acid concentration of thesulphated zirconia dioxide at a particle size of 3.1 nm between 0.005%and 0.1% caused an increase in the yield of light hydrocarbons.Concentrations greater than zero but less than 0.001% did not result inany change in yield relative to the control (0.0% acid concentration),an acid concentration of 0.1% resulted in a slightly better yield fordiesel than the yield for diesel at 0.06% concentration, and relativelylarge increases in acid concentrations above 0.1%, namely, 0.2% and 0.3%produced negligible differences in yield relative to the yield at 0.1%.Thus, concentrations larger than 0.1% may be used to improve the yieldof light hydrocarbons relative to the yield of the control, but notrelative to the yield at 0.1%.

TABLE 4 Effect of concentration, Sulphated zirconia dioxide, particlesize = 3.1 nm Concentration Fraction w/w % Petrol and sulphated zirconianaphtha Diesel Residue 0 16 27 57 0.001 16 27 57 0.005 18 29 53 0.01 2029 51 0.03 22 30 48 0.05 22 32 46 0.06 24 34 42 0.1 24 35 41 0.2 23 3442 0.3 24 35 41

The effect of the particle size at a given concentration was tested.Table 5 shows the yields and residue resulting from eleven differentparticle sizes of sulphated zirconia dioxide at 0.03% concentration. Theacid was added to crude oil at this concentration with varying particlesizes and the resulting mixtures were distilled as discussed above. Asshown, increasing the particle size between 3.1 nm and 7.6 nm did notsignificantly alter the yield of light hydrocarbons using 0.03%concentration of sulphated zirconia dioxide. Using an acid particle sizebetween 15 nm and 44 nm slightly impaired the yield of diesel, but onlycaused the residue fraction to increase from 48% to 49%. Increasing thesulphated zirconia dioxide particle size between 150 nm and 1100 nm moresignificantly impaired the yield of light hydrocarbons, but the yield inthis range was still better than that without use of the acid. Onlyparticle sizes greater than 10,000 nm resulted in light hydrocarbonyields which matched the hydrocarbon yields without use of the acid(e.g., 0% acid—the control of Table 4).

TABLE 5 Effect of particle size, Sulphated zirconia dioxide,concentration = 0.03 w/w % Fraction Petrol Particles size, nm andSulphated zirconia naphtha Diesel Residue 3.1 22 30 48 4.0 22 29 49 4.722 30 48 7.3 23 29 48 7.6 22 30 48 15 22 29 49 44 22 29 49 150 20 28 52600 17 29 54 1100 17 29 54 >10000 16 27 57

Example 3

Alumosilicate (acid) having a composition of SiO₂—66%, Al₂O₃—16%,Fe₂O₃—4%, MgO—10%, CaO—3%, and other components 1%, and a particle sizeof 30 nm was tested using the method of FIG. 1. As shown in Table 6below, increasing the concentration of alumosilicate at this particlesize from 0.001% to 0.05% resulted in increased yield of lighthydrocarbons, with the greatest increase relative to the control at andabove 0.05% acid concentration. It is noted that the yields of lighthydrocarbons at concentrations of 0.1% and 0.2% were identical to thatat 0.05%. Thus, concentrations larger than 0.05% of alumosilicate at aparticle size of 30 nm may be used to improve the yield of lighthydrocarbons relative to the yield of the control, but will causelittle, if any, improvement over the yield at 0.05%.

TABLE 6 Effect of concentration, alumosilicate, particle size = 30 nmFraction Concentration w/w % Petrol and alumosilicate naphtha DieselResidue 0 16 27 57 0.001 16 28 56 0.005 17 28 55 0.007 19 28 53 0.01 1932 49 0.03 20 32 48 0.05 21 33 46 0.1 21 33 46 0.2 21 33 46

Alumosilicates having a concentration of 0.03% were also added to crudeoil with varying particle sizes and the resulting mixtures weredistilled as discussed above. Table 7 shows the yields and residueresulting from seven different particle sizes of alumosilicates having aconcentration of 0.03%. As shown, a particle size of 30 nm provided thebiggest yield of light hydrocarbons relative to the control (0%alumosilicate—Table 6). Increasing the particle size from 30 nm to 70 nmcaused a drop in yield of light hydrocarbons, though the yield remainedgreater than that of the control. Increasing the particle size between70 nm and 150 nm caused a slight drop in Petrol and naphtha but a slightincrease in diesel. Increasing the particle size between 150 nm and 1200nm generally resulted in a relative decrease in yield of lighthydrocarbons, but still provided a yield which was greater than that ofthe control. A particle size greater than 10,000 nm did not provide abetter yield of light hydrocarbons than the control.

TABLE 7 Effect of particle size, Alumosilicates, concentration = 0.03w/w % Fraction Particles size, nm Petrol and alumosilicate naphthaDiesel Residue 30 20 32 48 70 20 30 50 150 19 31 50 400 19 27 54 700 1727 56 1200 17 27 56 >10000 16 27 57

Example 4

Zeolite A (sodium aluminum silicate) with a particle size of 20 nm wastested using the method of FIG. 1. As shown in Table 8, increasing theconcentration of Zeolite A at this particle size from 0.001% to 0.2%resulted in an increased yield of light hydrocarbons, with the greatestincrease relative to the control at and above 0.2%. It is noted that anincrease in acid concentration from 0.2% to 0.3% did not produce anychange in yield of light hydrocarbons. Thus, concentrations larger than0.2% of alumosilicate at a particle size of 20 nm may be used to improvethe yield of light hydrocarbons relative to the control, but notrelative to the yield at 0.2%.

TABLE 8 Effect of concentration, Zeolite A, particle size = 20 nmFraction Concentration w/w % Petrol and Zeolite A naphtha Diesel Residue0 16 27 57 0.001 16 28 56 0.005 19 29 52 0.01 20 30 50 0.05 21 31 48 0.122 31 47 0.2 22 32 46 0.3 22 32 46

Zeolite A having a concentration of 0.05% was also added to crude oilwith varying particle sizes and the resulting mixtures were distilled asdiscussed above. Table 9 below shows the yields and residue resultingfrom seven different particle sizes of Zeolite A at a concentration of0.05%. As shown, particle sizes of 20 nm and 50 nm provided the biggestyield of light hydrocarbons. Increasing the particle size from 50 nm to700 nm generally resulted in a decreased yield of light hydrocarbons,but still provided increased yield relative to the yield of lighthydrocarbons produced by the control (0% concentration of Zeolite Aacid—Table 8), and a particle size of 1200 nm and larger did not producean increased yield of light hydrocarbons relative to the control.

TABLE 9 Effect of particle size, Zeolite A, concentration = 0.05 w/w %Fraction Particles size, nm Petrol and Zeolite A naphtha Diesel Residue20 21 31 48 50 21 31 48 150 18 30 52 400 18 27 55 700 17 27 56 1200 1627 57 >10000 16 27 57

Example 5

Keggin hetero polyacid (H₃PMo₁₃O₄₀) with a particle size of 1 nm wastested using the method of FIG. 1. As shown in Table 10, increasing theconcentration of Keggin hetero polyacid at this particle size from0.001% to 0.2% resulted in an increased yield of light hydrocarbons,with the greatest increase relative to the control at and above 0.2%. Itis noted that an increase in acid concentration from 0.2% to 0.3% didnot produce any change in yield. Thus, concentrations larger than 0.2%of Keggin hetero polyacid at a particle size of 1 nm may be used toimprove the yield of light hydrocarbons relative to the control, but notrelative to the yield at 0.2%. In addition, as the yield of lighthydrocarbons at 0.001% acid concentration was greater than at 0% acidconcentration, it is anticipated that concentrations less than 0.001% ofKeggin hetero polyacid at a particle size of 1 nm may also be used toproduce a yield of light hydrocarbons better than that of the control(no acid), but less than that at 0.001%.

TABLE 10 Effect of concentration, H₃PMo₁₃O₄₀, particle size = 1 nmFraction Concentration w/w % Petrol and H₃PMo₁₃O₄₀ naphtha DieselResidue 0 18 31 51 0.001 18 33 49 0.005 20 37 43 0.01 21 40 39 0.05 2141 38 0.1 22 41 37 0.2 23 41 36 0.3 23 41 36

Example 6

Aluminum trichloride (AlCl₃) with a particle size of 100 nm was testedusing the method of FIG. 1. As shown in Table 11, increasing theconcentration of Aluminum trichloride at this particle size from 0.001%to 0.2% resulted in an increased yield of light hydrocarbons, with thegreatest increase relative to the control at and above 0.2%. It is notedthat increasing the concentration of acid from 0.2% to 0.3% did notproduce any change in yield relative to the yield at 0.2%. Thus,concentrations larger than 0.2% of Aluminum trichloride at a particlesize of 100 nm may also be used to improve the yield of lighthydrocarbons relative to the control but not relative to the yield at0.2%. In addition, as the yield of light hydrocarbons at 0.001%concentration was slightly greater than at 0% concentration, isanticipated that concentrations of Aluminum trichloride less than 0.001%may produce a yield marginally better than that of the control.

TABLE 11 Effect of concentration, AlCl₃, particle size = 100 nm FractionConcentration w/w % Petrol and AlCl₃ naphtha Diesel Residue 0 16 27 570.001 17 27 56 0.005 20 29 51 0.01 22 31 47 0.05 23 30 47 0.1 24 31 450.2 24 32 44 0.3 24 32 44

Aluminum trichloride having a concentration of 0.05% was also added tocrude oil with varying particle sizes and the resulting mixtures weredistilled as discussed above. Table 12 below shows the yields andresidue resulting from five different particle sizes of Aluminumtrichloride at a concentration of 0.05%. As shown, a particle size of100 nm provided the biggest yield of light hydrocarbons. Increasing theparticle size from 100 nm to 700 nm generally resulted in a decreasedyield of light hydrocarbons (mostly for Diesel), but still providedincreased yield relative to the yield of light hydrocarbons producedwithout any acid—the control (0% concentration of Aluminumtrichloride—Table 11), and particle sizes at 1200 nm and greater than10,000 nm did not produce a yield of light hydrocarbons in excess of thecontrol.

TABLE 12 Effect of particle size, AlCl₃, concentration = 0.05 w/w %Fraction Particles size, nm Petrol and AlCl₃ naphtha Diesel Residue 10021 31 48 400 20 30 50 700 20 25 55 1200 16 27 57 >10000 16 27 57

Example 7

Faujasite with a particle size of 30 nm was tested using the method ofFIG. 1. As shown in Table 13, increasing the concentration of Faujasiteat this particle size from 0.005% to 0.2% resulted in an increased yieldof light hydrocarbons, with the greatest increase relative to thecontrol at and above 0.2%. It is noted that increasing the concentrationof acid from 0.2% to 0.3% and to 0.4% did not produce any change in theyield of light hydrocarbons relative to the yield at 0.2%. Thus, acidconcentrations larger than 0.2% of Faujasite at a particle size of 30 nmmay also be used to improve the yield of light hydrocarbons relative tothat of the control but not relative to that at 0.2%. In addition, asthe yield of light hydrocarbons at 0.005% concentration was slightlygreater than at 0% concentration (for Diesel), it is anticipated thatconcentrations of Faujasite less than 0.005% may produce a yield betterthan that of the control and less than that at 0.005% (for Diesel). Itis further noted that different results were obtained using Faujasiteand Zeolite Y. Comparison of the results for Faujasite and Zeolite Yshows a higher yield of petrol and naphta, as well as diesel, forZeolite Y. This difference may be associated with differences in theacidic properties of these solid acids. In particular, the surfaceconcentration of acid sites of Faujasite and Zeolite Y responsible forconversion of heavy hydrocarbons to light hydrocarbons, as well as theirrespective accessibility or strength, are different for Faujasite andZeolite Y. Increasing the surface concentration of acid cites, strengthor accessibility increases the yield of light hydrocarbons.

TABLE 13 Effect of concentration, Faujasite, particle size = 30 nmFraction Concentration w/w % Petrol and Faujasite naphtha Diesel Residue0 16 27 57 0.005 16 29 55 0.01 17 30 53 0.03 19 29 52 0.05 19 31 50 0.120 31 49 0.2 20 32 48 0.3 20 32 48 0.4 20 32 48

Faujasite having a concentration of 0.05% was also added to crude oilwith varying particle sizes and the resulting mixtures were distilled asdiscussed above. Table 14 below shows the yields and residue resultingfrom six different particle sizes of Faujasite at a concentration of0.05%. As shown, a particle size of 30 nm provided the biggest yield oflight hydrocarbons. Increasing the particle size from 30 nm to 700 nmgenerally resulted in a decreased yield of light hydrocarbons (mostly ofDiesel), but still provided increased yield relative to the yield oflight hydrocarbons produced without any acid—the control (0%concentration of Faujasite—Table 13). Increasing the particle size from700 nm to 1200 nm caused a slight drop in petrol and naphtha but aslight increase in diesel, and thus no significant overall change to theresidue fraction. Particle sizes greater than 10,000 nm did not producea yield of light hydrocarbons in excess of the control.

TABLE 14 Effect of particle size, Faujasite, concentration = 0.05 w/w %Fraction Particles size, nm Petrol and Faujasite naphtha Diesel Residue30 19 31 50 150 19 29 52 400 17 29 54 700 19 25 56 1200 18 26 56 >1000016 27 57

Example 8

HZSM-5 with a particle size of 50 nm was tested using the method ofFIG. 1. As shown in Table 15, increasing the concentration of HZSM-5 atthis particle size from 0.005% to 0.2% resulted in an increased yield oflight hydrocarbons, with the greatest increase relative to the controlat and above 0.2%. It is noted that increasing the concentration of acidfrom 0.2% to 0.3% did not produce any change in the yield of lighthydrocarbons relative to the yield at 0.2%. Thus, acid concentrationslarger than 0.2% of HZSM-5 at a particle size of 50 nm may also be usedto improve the yield of light hydrocarbons relative to that of thecontrol but not relative to that at 0.2%. In addition, as the yield oflight hydrocarbons at 0.005% concentration was slightly greater than at0% concentration (for Diesel), it is anticipated that concentrations ofHZSM-5 less than 0.005% may produce a yield better than that of thecontrol and less than that at 0.005% (for Diesel).

TABLE 15 Effect of concentration, HZSM-5, particle size = 50 nm FractionConcentration w/w % Petrol and HZSM-5 naphtha Diesel Residue 0 16 27 570.005 16 28 56 0.01 17 29 54 0.04 17 29 54 0.05 17 31 52 0.1 18 30 520.2 18 31 51 0.3 18 31 51

HZSM-5 having a concentration of 0.05% was also added to crude oil withvarying particle sizes and the resulting mixtures were distilled asdiscussed above. Table 16 below shows the yields and residue resultingfrom six different particle sizes of HZSM-5 at a concentration of 0.05%.As shown, a particle size between 50 nm and 400 nm provided the biggestyield of light hydrocarbons. Increasing the particle size from 400 nm to1200 nm resulted in a decreased yield of light hydrocarbons, but stillprovided increased yield relative to the yield of light hydrocarbonsproduced without any acid—the control (0% concentration of HZSM-5—Table15). It is also noted that the yield of light hydrocarbons at 50 nm isgreater than that of the control (no acid). Thus, particle sizes lessthan 50 nm are likely also to improve the yield of light hydrocarbons atthis acid concentration of HZSM-5. Particle sizes greater than 10,000 nmdid not vary the yield of light hydrocarbons relative to the control.

TABLE 16 Effect of particle size, HZSM-5, concentration = 0.05 w/w %Fraction Particles size, nm Petrol and HZSM-5 naphtha Diesel Residue 5017 31 52 150 17 30 53 400 17 31 52 700 16 30 54 1200 16 29 55 >10000 1627 57

Example 9

Mordenite with a particle size of 150 nm was tested using the method ofFIG. 1. As shown in Table 17, increasing the concentration of Mordeniteat this particle size from 0.005% to 0.05% resulted in an increasedyield of light hydrocarbons (mostly of Diesel), with the greatestincrease relative to the control at and above 0.05%. It should be notedthat increasing the acid concentration from 0.05% to 0.1%, and 0.2% didnot produce any change in the yield of light hydrocarbons relative tothe yield at 0.05%. Thus, acid concentrations larger than 0.05% ofMordenite at a particle size of 150 nm may also be used to improve theyield of light hydrocarbons relative to that of the control but notrelative to that at 0.05%. In addition, as the yield of lighthydrocarbons at 0.005% concentration was slightly greater than at 0%concentration (for Diesel), it is anticipated that concentrations ofMordenite less than 0.005% may produce a yield better than that of thecontrol and less than that at 0.005% (for Diesel).

TABLE 17 Effect of concentration, Mordenite, particle size = 150 nmFraction Concentration w/w % Petrol and Mordenite naphtha Diesel Residue0 16 27 57 0.005 16 28 56 0.01 17 29 54 0.04 17 32 51 0.05 17 33 50 0.117 33 50 0.2 17 33 50

Mordenite having a concentration of 0.05% was also added to crude oilwith varying particle sizes and the resulting mixtures were distilled asdiscussed above. Table 18 below shows the yields and residue resultingfrom five different particle sizes of Mordenite at a concentration of0.05%. As shown, increasing the particle size from 100 nm to 1200 nm atthis concentration resulted in a decreased yield of light hydrocarbons(mostly Diesel), but still produced a yield of light hydrocarbons inexcess of the control (0% concentration of Mordenite—Table 17). Inaddition, it is noted that the yield of light hydrocarbons was greaterat a particle size of 100 nm and at a particle size of greater than10,000 than it was for the control. Thus, it is anticipated thatparticle sizes smaller than 100 nm and larger than 10,000 may also beused at this concentration of Mordenite acid to improve the yield oflight hydrocarbons relative to the control.

TABLE 18 Effect of particle size, Mordenite, concentration = 0.05 w/w %Fraction Particles size, nm Petrol and Mordenite naphtha Diesel Residue100 17 33 50 400 17 31 52 800 17 29 54 1200 16 29 55 >10000 16 28 56

Example 10

MCM-41 with a particle size of 50 nm was tested using the method ofFIG. 1. As shown in Table 19, increasing the concentration of MCM-41 atthis particle size from 0.005% to 0.05% resulted in an increased yieldof light hydrocarbons with the maximum yield at an acid concentration atand above 0.04%. It is noted that the yield of light hydrocarbons usinga concentration of 0.005% was identical to that of the control (0%concentration of MCM-41). In addition, increasing the acid concentrationfrom 0.04% to 0.1% and 0.2% did not have any effect on the yield oflight hydrocarbons at this particle size—the yield of light hydrocarbonssimply remained at its highest level. Thus, acid concentrations largerthan 0.05% of MCM-41 at a particle size of 50 nm may also be used toimprove the yield of light hydrocarbons relative to that of the controlbut not relative to that at 0.05%.

TABLE 19 Effect of concentration, MCM-41, particle size = 50 nm FractionConcentration w/w % Petrol and MCM-41 naphtha Diesel Residue 0 16 27 570.005 16 27 57 0.01 16 29 55 0.04 16 30 54 0.05 17 29 54 0.1 17 29 540.2 17 29 54

MCM-41 having a concentration of 0.05% was also added to crude oil withvarying particle sizes and the resulting mixtures were distilled asdiscussed above. Table 20 below shows the yields and residue resultingfrom six different particle sizes of MCM-41 at a concentration of 0.05%.As shown, increasing the particle size from 50 nm to 700 nm at this acidconcentration resulted in a generally constant yield of lighthydrocarbons which was higher than the yield of the control (0%MCM-41—Table 19). It is noted that the fraction of light hydrocarbonsyielded at a particle size of 50 nm and at a particle size of 1200 wasgreater than it was for the control. At particle sizes greater than10,000 nm, the yield was the same as it was for the control. Thus, it isanticipated that particle sizes less than 50 nm and particle sizesgreater than 1200 nm may also be used at this concentration of acid toimprove the yield of light hydrocarbons relative to the control.

TABLE 20 Effect of particle size, MCM-41, concentration = 0.05 w/w %Fraction Particles size, nm Petrol and MCM-41 naphtha Diesel Residue 5017 29 54 150 16 29 55 400 17 29 54 700 16 30 54 1200 16 28 56 >10000 1627 57

The above tables clearly show a general trend in which increasing theconcentration of the nanoparticles of a given solid acid between 0.005%and 0.2% causes a general increase in yield of light hydrocarbons withthe biggest increases occurring toward, and likely above, the upper endof this range. The above tables also reveal a general trend in whichusing a characteristic acid particle size ranging from 3 nm to 1200 nmwith acid concentration values of 0.03% to 0.05% maintained the yield oflight hydrocarbons above that of the control, the biggest yieldsrelative to the control occurring with use of the smallest particlesizes. Based on this data, it is believed that the best way to maximizeyield of light hydrocarbons is to use the smallest nanometer particlesize available for a given acid and the highest concentration within therange outlined above for the given acid. It will be appreciated thatacid particle size and acid concentration are offsetting factors, andthus that different combinations of acid particle size and acidconcentration may produce the same yield of light hydrocarbons providedthat the acid particle size is not too large and/or the acidconcentration is not too small.

According to another aspect of the invention, when nanoparticles ofdifferent acids are mixed with crude oil prior to initial distillation,the increased yield of light hydrocarbons after distillation isgenerally additive. For example, as shown below in Table 21, HZSM-5 at0.02% concentration with a particle size of 43 nm was mixed with MCM-41at 0.02% concentration with a particle size of 50 nm (which is close to43 nm) in crude oil prior to initial distillation. After initialdistillation, the fractional yield was 16% petrol/naphtha; 30% diesel;and 54% residue. HZSM-5 at 0.04% concentration (e.g. twice as much) witha particle size of 50 nm was then mixed by itself in crude oil prior toinitial distillation—this produced a fractional yield of 17%petrol/naphtha (a slight increase); 29% diesel (a slight decrease); and54% residue (identical). In addition, MCM-41 at 0.04% concentration(e.g., twice as much) with a particle size of 50 nm was then mixed byitself in crude oil prior to initial distillation—this produced afractional yield of 16% petrol/naphtha (identical); 30% diesel(identical); and 54% residue (identical). Thus, it may be inferred thatthe combination of HZSM-5 and MCM-41 mixed with the crude oil prior toinitial distillation had an additive effect.

Similarly, when acids of small particle size are mixed with acids oflarge particle size, the results can be additive in the sense that theacid of smaller particle size tends to improve the yield of lighthydrocarbons more than the acid of larger particle size, and thecombination provides a result which is in between what is obtained withusing either the small particle size additive alone or the largeparticle size additive alone. For example, as shown in Table 21, whensulphated zirconia of 0.025% concentration with a particle size of 3.1nm was mixed with Mordenite of 0.025% concentration with a particle sizeof 100 nm in crude oil prior to initial distillation, the fractionalyield after initial distillation was 19% petrol/naphtha; 33% diesel; and48% residue. Sulphated zirconia of 0.05% concentration (e.g., twice asmuch) with a particle size of 3.1 nm was then mixed with crude oil byitself prior to initial distillation, and the fractional yield afterinitial distillation was 22% petrol/naphtha (higher); 32% diesel(slightly lower); and 46% residue (lower). Mordenite of 0.05%concentration (e.g., twice as much) with a particle size of 100 nm wasthen mixed with crude oil by itself prior to initial distillation, andthe fractional yield after initial distillation was 17% petrol/naphtha(lower); 33% diesel (the same); and 50% residue (higher). Thus, using anacid with a larger particle size in combination with an equal amount ofa different acid of smaller particle size produced a smaller yield oflight hydrocarbons than that produced by simply using twice as much ofthe acid with the smaller particle size. This is expected since, asdiscussed above, improved yield is inversely related to the acidparticle size within the relevant range.

On the other hand, as seen below in Table 21, when sulphated zirconia of0.015% concentration with a particle size of 3.1 nm was mixed withalumosilicate of 0.015% having a particle size of 700 nm in crude oilprior to initial distillation, the fractional yield after initialdistillation was 22% petrol/naphtha, 32% diesel, and 46% residue. Thiscompared favorably with respect to the addition of sulphated zirconia ofparticle size 3.1 nm in an amount of 0.03% (e.g., twice as much) whichgave a yield of 22% petrol/naphtha (same), 30% diesel (slightly lower),and 48% residue (slightly higher). Likewise, it compared favorably withrespect to the addition of 0.03% alumosilicate 700 nm, which gave ayield 17% petrol/naphtha (much lower), 27% diesel (much lower), and 56%residue (much higher). Effectively then, the combination of 3.1 nmsulphated zirconia with the 700 nm alumosilicate was synergistic andprovided even better results than the unexpected results obtained whenadding nanoparticles of a single acid to the crude oil prior to initialdistillation.

Synergistic results were also found when aluminum trichloride 100 nmnanoparticles were mixed with 800 nm Mordenite nanoparticles with eachconstituting 0.025% by weight in the crude oil prior to initialdistillation (both of the nanoparticles being relatively large). As seenin Table 21, the fractional yield after initial distillation was 23%petrol/naphtha, 31% diesel, and 46% residue. This compared favorablywith respect to the addition of aluminum trichloride of particle size100 nm in an amount of 0.05% (e.g., twice as much) which gave a yield of23% petrol/naphtha (same), 30% diesel (slightly lower), and 47% residue(slightly higher). Likewise, it compared favorably with respect to theaddition of 0.05% Mordenite 800 nm which gave a yield 17% petrol/naphtha(much lower), 29% diesel (lower), and 54% residue (much higher). Theinventors believe that nonadditive increases in the yield of lighthydrocarbons for some mixtures may be caused by strong interaction ofthe mixing components. For mixture of sulphated zirconia andalumosilicate or for mixture of aluminum trichloride and mordenite, itis believed that interaction of nanophased components leads to aformation of nanophased interfacial structure where strong acid sitesare located. These acid sites are characterized by the highest ofcatalytic activity with regard to cracking of heavy hydrocarbons. As aresult, it is believed that the yield of light hydrocarbons increasesnonadditively.

TABLE 21 Additive effect of different solid acids Fraction PetrolConcentration Concentration w/w % and w/w % Additive 1 Additive 2naphtha Diesel Residue Mixture works additively HZSM-5 50 nm MCM-41 50nm 0.02 16 30 54 0.02 HZSM-5 50 nm — 17 29 54 0.04 — MCM-41 50 nm 0.0416 30 54 Sulphated zirconia Mordenite 100 nm 19 33 48 3.1 nm 0.025 0.025Sulphated zirconia 22 32 46 3.1 nm 0.05 Mordenite 100 nm 17 33 50 0.05Mixture works synergistically Sulphated zirconia Alumosilicate 22 32 463.1 nm 0.015 700 nm 0.015 Sulphated zirconia 22 30 48 3.1 nm 0.03Alumosilicate 17 27 56 700 nm 0.03 AlCl₃ 100 nm 0.025 Mordenite 800 nm23 31 46 0.025 AlCl₃ 100 nm 0.05 23 30 47 Mordenite 800 nm 17 29 54 0.05

It will be appreciated by those skilled in the art that Table 21 isrepresentative of just a few of the combinations that can be made, andthat many other combinations of nanoparticles of different acids can bemade with the same or different sizes, and that the concentrations andparticle sizes utilized for each can be modified.

It has been shown that the addition of solid acid nanoparticles intocrude oil prior to initial distillation increases the resulting yield oflight hydrocarbons (e.g., gasoline and diesel) during initialdistillation. It is believed that the increased yield is due tocatalytic low temperature cracking. It is also believed that theaddition of the solid acid nanoparticles is environmentally benign.

Turning now to FIG. 2, according to a second method for implementing theinvention, at step 110, solid acid nanoparticles (e.g., sulphatedzirconia dioxide) are added to and mixed into hexane. At step 115,ultrasound is used to distribute the solid acid nanoparticles in thehexane and generate a colloidal solution. The hexane-nanoparticlecolloidal solution is then added at step 118 to crude oil and mixed. Byway of example only, 0.1 ml or colloidal solution may be added to 100 mlof crude oil. At step 120, the crude oil with the colloidal solution issubjected to a first stage distillation. The result of the first stagedistillation, as described above, is that a larger yield of gasoline anddiesel (light hydrocarbons) is obtained than would otherwise be obtainedif the solid acid nanoparticles had not been added to the crude oil. Aspreviously stated, it is believed that the nanoparticles act tocatalytically crack some of the larger molecule hydrocarbons atrelatively low temperatures (i.e., the distillation temperatures ofgasoline and diesel).

According to another aspect of the invention, solid acid micropowdersare added to a crude oil fraction that remains after a partial initialdistillation of the crude oil to remove gas, gasoline and optionallycrude oil. The solid acid micropowders are mixed into the remainingcrude oil fraction before the crude oil fraction is subjected toadditional distillation. Thus, as seen in FIG. 3, at step 205, crude oilis subject to partial first stage distillation up to approximately 350°C. or 360° C. to obtain gases, gasoline (petrol) and diesel, and aresidue crude oil fraction. Then, at step 210, thenanoparticles/micropowder is added to and mixed into the residue crudeoil fraction and at 220 the mixture of thenanoparticles/micropowder/residue fraction are subjected to completionof the first stage distillation (typically by boiling up to 420° C.).The result of the first stage distillation, as described in more detailbelow, is that an increased yield of light hydrocarbons are obtainedthan would otherwise be obtained if the nanoparticles/micropowder hadnot been added.

Using the method of FIG. 3, samples of crude oil residue fractions(e.g., the crude oil already having had the gasoline and dieseldistilled out in a standard manner by subjecting the crude oil totemperatures between 350° C. and 360° C.) were tested with differentnanoparticles/micropowders or additive combinations. After the partialinitial distillation, the addition to the residue ofnanoparticles/micropowders of solid acids and combinations thereof, withdifferent sized particles and different concentrations, such asdiscussed above with reference to Tables 1-21 (but not limited thereto),yielded additional yields of light hydrocarbons.

TABLE 22 Yield of light hydrocarbons by heating the residue at 420° C.in the presence of nanoparticles/micropowders. nanoparticles/micropowderconcentration Yield, % — — 3 Zeolite A 400 nm 0.025 26 Alumosilicate0.025 22 Mordenite 100 nm 0.01 17 HZSM-5 50 nm 0.01 24 Sulphatedzirconia 3.1 nm 0.001 17 AlCl₃ 100 nm 0.05 27 MCM-41 400 nm 0.01 21H₃PMo₁₃O₄₀ 0.001 22 Mordenite 800 nm 0.01 41 AlCl₃ 100 nm 0.01

As illustrated above in Table 22, solid acid micropowders of all of thesolid-acids discussed above with respect to Tables 1-21 (except forZeolite Y and Faujasite) were each added to a respective sample residuefraction of crude oil which had been subjected to crude oil temperaturesbetween 350° C. and 360° C. Each micropowder/residue mixture was thenboiled up to 420° C. Without exception, these trials producedsignificant yields of light hydrocarbons (naphta/petrol and diesel) fromtheir respective residue fractions, even when relatively smallconcentrations were utilized. For example, H₃PMo₁₃O₄₀ at a concentrationof just 0.001 produced a yield of 22% light hydrocarbons from a residuefraction, and sulphated zirconia with a particle size of 3.1 nm and aconcentration of just 0.001 produced a yield of 17% light hydrocarbonsfrom a residue fraction. Mordenite at a concentration of just 0.01produced a yield of 17% light hydrocarbons from a residue fraction in afirst trial using a particle size of 100 nm, and a yield of 41% lighthydrocarbons from a residue fraction in a second trial using a particlesize of 800 nm in conjunction with AlCl₃ having a particle size of 100nm and also present in a concentration of 0.01. MCM-41 with a particlesize of 400 nm at a concentration of 0.01 produced a yield of 21% lighthydrocarbons from a residue fraction. HZSM-5 with a particle size of 50nm at a concentration of 0.01 produced a yield of 24% light hydrocarbonsfrom a residue fraction. Thus, relatively small concentrations andrelatively larger particle sizes still produced significant yields oflight hydrocarbons from a residue fraction of crude oil. Largerconcentrations of solid acids also produced significant yields of lighthydrocarbons from a residue fraction of crude oil. AlCl₃ with a particlesize of 100 nm at a concentration of 0.05 produced a yield of 27% lighthydrocarbons from a residue fraction. Alumosilicate at a concentrationof 0.025 produced a yield of 22% light hydrocarbons from a residuefraction. Zeolite A with a particle size of 400 nm at a concentration of0.025 produced a yield of 26% light hydrocarbons from a residuefraction.

It will be appreciated that as the yields of light hydrocarbons listedin Table 22 were produced from residue fractions following a partialstandard distillation at temperatures between 350° C. and 360° C., suchyields were additional to those produced from the original samples ofcrude oil during the partial initial distillation without the solidacids, which accounted for roughly 16% petrol/naphta, 27% Diesel, and57% Residue (43% light hydrocarbons, 57% Residue) of the original crudeoil samples as discussed above. For example, since Sulphanated zirconiaat 3.1 nm in a concentration of 0.001 produced a yield of 17% lighthydrocarbons from the residue fraction, the total percentage of lighthydrocarbons produced from the original crude oil sample correspondingto this particular test was roughly 53%:

(43% light hydrocarbons from partial initialdistillation)+(0.17)*(57%))=53% total light hydrocarbons.

Similarly, since Zeolite A at 400 nm in a concentration of 0.025produced a yield of 26% light hydrocarbons from the residue fraction,the total percentage of light hydrocarbons produced from the originalcrude oil sample corresponding to this particular test was roughly 57%:

(43% light hydrocarbons from partial initialdistillation)+(0.26)*(57%))=57% total light hydrocarbons.

By contrast, the inventors have found that simply heating the originalcrude oil to 420° C. without adding any solid acids produced a yield of45%, slightly higher than the 43% produced by heating the original crudeoil to between 350° C. and 360° C., but far less than the total lighthydrocarbons produced by adding solid acids to the residue fractionsafter the partial initial standard distillations.

There have been described and illustrated herein several embodiments ofmethods for increasing the light fraction output of a crude oildistillation by adding nanoparticles of solid acids, solid acidmicropowder, and combinations thereof to the crude oil. While particularembodiments of the invention have been described, it is not intendedthat the invention be limited thereto, as it is intended that theinvention be as broad in scope as the art will allow and that thespecification be read likewise. Thus, while particular solid acids,micropowders, and combinations thereof have been disclosed, it will beappreciated that other acids, solid acids, micropowders, andcombinations thereof could be used as well. Also, while certain rangesof concentrations of solid acids have been described, it will berecognized that other concentrations and weight percentages could beutilized. Furthermore, while specific sizes of nanoparticles of solidacid have been described, it will be understood that other sizednanoparticles can be similarly utilized. It will therefore beappreciated by those skilled in the art that yet other modificationscould be made to the provided invention without deviating from itsspirit and scope as claimed.

1. A method of increasing distillate yield in a crude oil distillation,comprising: prior to distillation of crude oil, adding a plurality ofsolid acid nanoparticles of diameter between 3 nm and 1200 nm to thecrude oil to create a crude oil/nanoparticle mixture, the solid acidnanoparticles comprising a weight percentage of the crudeoil/nanoparticle mixture between 0.001% and 0.2%; and distilling saidcrude oil/nanoparticle mixture to generate at least one lighthydrocarbon and a residue, whereby said residue generated fromdistilling said crude oil/nanoparticle mixture is smaller than a residuewhich would be generated from an identical distillation of the crude oilwithout said solid acid nanoparticles added thereto.
 2. A methodaccording to claim 1, wherein: said plurality of solid acidnanoparticles are chosen from at least one of sulphated zirconia,alumosilicate, Zeolite A, Zeolite Y, keggin acid, aluminum trichloride,Faujasite, HZSM-5, Mordenite, and mcm-41.
 3. A method according to claim1, wherein: said plurality of solid acid nanoparticles which comprisesaid weight percentage are no more than 150 nm in diameter.
 4. A methodaccording to claim 3, wherein: said solid acid nanoparticles whichcomprise said weight percentage are no more than 100 nm in diameter. 5.A method according to claim 4, wherein: said solid acid nanoparticleswhich comprise said weight percentage are no more than 50 nm indiameter.
 6. A method according to claim 5, wherein: said solid acidnanoparticles which comprise said weight percentage are no more than 20nm in diameter.
 7. A method according to claim 1, wherein: said weightpercentage of said solid acid nanoparticles in said crudeoil/nanoparticle mixture is at least 0.005%.
 8. A method according toclaim 7, wherein: said weight percentage of said solid acidnanoparticles in said crude oil/nanoparticle mixture is at least 0.01%.9. A method according to claim 8, wherein: said weight percentage ofsaid solid acid nanoparticles in said crude oil/nanoparticle mixture isat least 0.03%.
 10. A method according to claim 9, wherein: said weightpercentage of said solid acid nanoparticles in said crudeoil/nanoparticle mixture is at least 0.05%.
 11. A method according toclaim 10, wherein: said weight percentage of said solid acidnanoparticles in said crude oil/nanoparticle mixture is at least 0.1%.12. A method according to claim 1, wherein: said plurality of solid acidnanoparticles are sulphated zirconia, have a diameter of between 3 nmand 4 nm, and comprise a weight percentage of the crude oil/nanoparticlemixture of at least 0.1%.
 13. A method according to claim 1, wherein:said plurality of solid acid nanoparticles are H₃PMo₁₃O₄₀, have adiameter of substantially 1 nm, and comprise a weight percentage of thecrude oil/nanoparticle mixture of at least 0.1%.
 14. A method ofincreasing yield of hydrocarbons from a crude oil, said methodcomprising: subjecting the crude oil to a partial initial distillationby heating the crude oil to a temperature between 350° C. and 360° C. togenerate an initial quantity of light hydrocarbons and a residue fromthe crude oil; adding nanoparticles of a solid acid micropowder to theresidue of the partially distilled crude oil to create a partiallydistilled crude oil residue/solid acid micropowder mixture; andcompleting the initial distillation of the crude oil by heating saidmixture to a temperature above 360° C. and below 450° C. and distillingsaid mixture to generate additional light hydrocarbons therefrom,whereby the total light hydrocarbons generated from the initial partialdistillation and the completing of the initial distillation is largerthan the total light hydrocarbons which would be generated from anidentical initial distillation of the crude oil without said solid acidmicropowder.
 15. A method according to claim 14, wherein: said solidacid micropowder is chosen from Zeolite A, Alumosilicate, Mordenite,Sulphated zirconia, aluminum trichloride, MCM-41, H₃PMo₁₃O₄₀, and HZSM-5micropowder.
 16. A mixture consisting essentially of: crude oil in aweight percentage between 99.999% and 99.8%; and a plurality of solidacid nanoparticles having a weight percentage between 0.001% and 0.2%and having respective diameters between 3 nm and 1200 nm.
 17. A mixtureaccording to claim 16, wherein: said nanoparticles have respectivediameters of no more than 150 nm.
 18. A mixture according to claim 17,wherein: said nanoparticles have respective diameters of no more than 50nm.
 19. A mixture according to claim 16, wherein: said plurality ofsolid acid nanoparticles comprise a weight percentage of said mixture ofat least 0.005%.
 20. A method according to claim 19, wherein: saidplurality of solid acid nanoparticles comprise a weight percentage ofsaid mixture of at least 0.01%.
 21. A method according to claim 20,wherein: said plurality of solid acid nanoparticles comprise a weightpercentage of said mixture of at least 0.03%.
 22. A method according toclaim 21, wherein: said plurality of solid acid nanoparticles comprise aweight percentage of said mixture of at least 0.05%.
 23. A methodaccording to claim 22, wherein: said plurality of solid acidnanoparticles comprise a weight percentage of said mixture of at least0.1%.
 24. A method of increasing distillate yield in a crude oildistillation, comprising: prior to distillation of crude oil, addinghexane and a plurality of solid acid nanoparticles of diameter between 3nm and 1200 nm to the crude oil to create a crudeoil/hexane/nanoparticle mixture; and distilling the crudeoil/hexane/nanoparticle mixture to generate at least one lighthydrocarbon and a residue, whereby said residue generated fromdistilling said crude oil/hexane/nanoparticle mixture is smaller than aresidue which would be generated from an identical distillation of thecrude oil without said hexane and said solid acid nanoparticles addedthereto.
 25. A method of increasing distillate yield in a crude oildistillation, comprising: prior to distillation of crude oil, adding aplurality of solid acid nanoparticles of diameter between 3 nm and 1200nm to the crude oil to create a crude oil/nanoparticle mixture, thesolid acid nanoparticles comprising a weight percentage of the crudeoil/nanoparticle mixture greater than 0.001% and distilling said crudeoil/nanoparticle mixture to generate a fractional amount of hydrocarbonsand a fractional amount of residue, whereby said fractional amount ofhydrocarbons generated from distilling said crude oil/nanoparticlemixture is larger than a fractional amount of hydrocarbons which wouldbe generated from an identical distillation of the crude oil withoutsaid solid acid nanoparticles added thereto.
 26. A method according toclaim 25, wherein: said weight percentage of said solid acidnanoparticles in said crude oil/nanoparticle mixture is no more than0.2%.